Azo dyes and method for their preparation



Patented July 28, 1936 2,048,844 szo nuns Ann Mar-non res. rm

PREPARATIION Miles A. Dahlen and Robert E. Etneller, Wilmington, Del, assignors to E. I. du Pont de Nemours& Company, Wilmington, Bet, a carporation of Delaware No Drawing. Application June 22,1933,

Serial No.

23 Clas.

XCONHarylene-N=NA in which X represents a hydroaromatic nucleus,

arylene represents an arylene nucleus and A lent fastness thereto.

represents the residue of an ice color coupling component.

It is an object of the present invention to prepare new ice colors, which may be developed on the fibers and impart attractive shades of excel- A further object is to produce new and desirable shades, particularly bluish-red, Bordeaux, violet and blue. A still further object is to prepare water and alkali-insoluble pigments. Additional objects will become apparent from a consideration of the following description.

These objects are attained according to the herein described invention wherein arylamines of the following general formula:

are diazotized and coupled with ice colorcoupling components. In the aforementioned formula the terms X and arylene have the same meaning as previously given. In its preferred embodiment X represents a hydroaromatic nucleusof the cyclohexane or decahydronaphthalene series, and arylene represents an arylene nucleus of the benzene or naphthalene series. Both of these components should be free from groups which render the resulting dyestuffs wateror alkalisoluble, such as carboxylic and sulfonic acid groups. With the exception of solubilizing groups, these components may have other groups substituted thereon, for instance the component designated by X may have substituted thereon alkyl, alkoxyl, aralkyl, aryl and aryloxyl groups; and the component designated by arylene may have substituted thereon alkyl, alkoxyl and halogen groups.

The invention may be more completely understocd by a consideration of the following illustrative examples in which the quantities are stated in parts by weight:

Example 1 Cotton skeins, impregnated in the usual manner with the beta-naphthalide of 2,3-hydroxynaphthoic acid, were developed in a diazo bath prepared as follows:

21.8 parts of N,-hexahydrobenzoyl-p-phenylenee swine (Cl. Mil -=36) diamine were stirred with 30 parts of hydrochloric acid of 30% strength and-350 parts of cold water, and the base diazotized with '7 parts of sodium nitrite dissolved in 30 parts of water. When the diazotization was complete, the solution was filtered and the mineral acidity neutralized with sodium acetate.

When the development of the color in the above bath was complete, the skeins were rinsed, soaped at the boil, rinsed and dried.

By this process a bright red=Bordeaux dyestuil of the probable structure:

one-n,

/CH: CHa-CHQ is obtained. The color possessedgood fastness to washing and light.

Example 2 Cotton skeins, padded with asolution of B- naphthol in caustic, were developed in a diazo solution prepared as in Example 1. When the development was complete,- the skeins were rinsed, soaped at the boil, rinsed and dried. An orange dyeing of good fastness to washing was obtained.

The dyestuif has the probable formula:

/CH1 CHPCH OH Example 3 When the diazotization was complete, the solution,

was filtered and the mineral acidity neutralized with sodium acetate.

bath was complete, the skeins were rinsed, soaped at the boil, rinsed and dried. By this process a red dyestuif of good fastness to wash- -6 ing and fairwfastness to lightwas obtained. The

' dyestufl has the probable formula:

oat-om NHC o-cn on,

Examples 20 Cotton skeins, padded in the usual manner with the p-chlor-anilide of 2-hydroxy-carbazole- 3-carboxylic acid, were developed in the diazo bath prepared as in Example 3.

After the development, and the rinsing and 25 soaping offthe skeins, a brown dyeing of good .fastness to light and washing was obtained. The

dyestufl has the probable formula:

Cotton -slreins, padded in the usual manner with the beta-naphthalide of- 2,3-hydroxy-naph- 4 thoic' acid, were developed in a diazo bath pre- 7 pared as follows:

24.8 parts .of 4-hexahydrobenzoylamino-3- methoxy-aniline' were stirred with 30 parts of hydrochloric acid of 30% strength and.350 parts 4 of cold'water, "and the base diazotized with 7 parts ;of sodium nitrite, dissolved in 30 parts, of water. The diazo solution was filtered and the mineral acidity neutralized with sodium acetate or sodium carbonate. 50 "After the development in the above bath, and the rinsing and soaping of the skeins, a Bordeaux dyeing of good fastness to washing and fair fastness to light was obtained. The dye probably the following formula:

' oom orig-011 NHQO-C 0H5' 70 I CHr-GH:

when thedevelopment of the color in the above" I Example 6 Cotton skeins, padded in the usual manner with the anilide of 2,3-hydroxy-naphthoic acid, were developed in a diazo bath prepared as follows! 27.8 parts of 4-hexahydrobenzoylamino-2,5-di methoxy-aniline were stirred in 30 parts of hydrochloric acid of 30% strength and 350 parts of cold water, and the base dlazotized with 'Zparts of sodium nitrite dissolved in 30 parts of water. The diazo solution was'filtered and the mineral acidity neutralized with sodiumcarbonate.

After the development, and the rin'sing' and soaping 0f the skeins, a bright blue dyeing of good fastness to light and washing-Wm obtained. The dyestufl has the probable formula:

(IDCHa Example 7 CII2-OH2 CHr-C H,

i c.-..c H1

NHC O-CH 0H,

CH CHr-CH:

CONH

Example 8 Cotton skeins, padded in the usual manner with the p-anisidide of 7-hydroxy-alpha nap htho-carbazole-6-carboxylie acid, were developed in the diazo bath prepared as in Example 6.

Afterthe-development, and the rinsing and soaping of the skeins, a blue dyeing of good fastness to washing and light was obtained. The dyestuil. probably has the following structure:

Example 9 Cotton skeins, padded with the beta-naphtha-' lide of 2-3-hydroxy-naphthoic acid, were developed in a diazo bath prepared from 23.2'parts of N- (hexahydro -p-toluyl-) p-phenylene-diamine by the'method given in Example 1. After the development, and the rinsing and soaping of the skeins, a red dyeing of good fastness to. washing gone and fair tastness to light was obt'elned. a" stufi probably has the lollowln: 10mph:

- Ci rd -01! v CONE Emmple lo 1 Cotton skelns, padded 1mm the bee-firmwllde of 2-3-hydroxy-naphtholc acld, wredeveloped in a. dlazo bath prepared from-124:8 ports of N-(hexahydro-p-anlsolrb)p phenyle diamine by the method given in Ejkamp'le'lifMter the development,-and 1 1 -153 manta-height the skelns, a red ye m 8 m to woshing and falr'tasmes m nghvmflbtma The dyestufl' probably has the following comm Eqqmple ll Cotton skelns, imoreg n ted rheuner with the para enlsldlde or 2,8"-' l lydroxynaphtholc acid; were developed}; hQf'fdlam baph prepared from 21.8 partd 'qt N-h'l iahyilrobehzoylm-phenylene-dlalnlne by," the iihetlhcid in Example 1. Afier'the evelbmilimgfgnq the rai s ing and soapihg or the.'-skelns;a' s oarle t dyelxig light was obtal ed.

structure:

A; bHf OHa N=N NHCO-C cm G s-C I on o conaOocm Example 12 Cotton skeins, lledded m tneosuelm pni will; the beta-naphthallde of 2,3hydi:bxy-liaphtlolo acid, were developed ln a' dflfloihflh 'fpl'e' from 232 parts of '5-hekahy drobehioyllimlqo- 2-me thyl anlllne by the method -gl\rehf* lq,jatample 1. After the degelopmeilfi; and the 'i'higlng arid soaplng of the shelns, a lbrlght-i'eol dyeing of good lastness to light and washing wild obtglfled.

gm'n.

'- 1 ms:ems, podded la the usual manner with 'dl -aoeto ebetyl o-tolldlne. were developed in the dlezo both prepgred as in Example 12. After the Eleyelppment, end the: rinsing and soaplug, o! fithe skelng. a'brlg'h'q yellow dyelng of goodla'stbees telrlastness to llghtwas {lotion skelng; heeded ln' the usual menner the .bet'e-hdplithallde -bfi-zj hydroxy-naphtholc 'ge'ldgi v'ere eveloped-1h a dle'za -bd th prepared from;

- fliline were 'metihod'g'lveu in Example eplhl: of "me-midweeordeuux dyelhg of good t esfsltoweshlnf (l-light was obtained. The

ELmmplelS A solution ot=the anillde o! 2,3-hydroxy-napgtholeheld was brepared hystlrrln'g -10 Darts t th wee wlm-barts of dloohol', adding 25 m iot hydroxide-or 25%, strength and "m'pafrts of A dlaio solutloh,prepered iron; 4meihl ydmbedmylmmo-zxmmetnoxywee p am-eon in Example 6. An equiveledt'qu'pntl'tg o! the dlezo solutlon waa edded to eolfiflolr "of the onlllde, resllltlhg 'lncoubllng thellnsoluble-olgment possessing the lollowing commotion v Y 'cmo' wit solution. i'abric was rinsed, soaped, rinsed and dried. The

Example 16 printed pattern showed good fastness to light and 5 Cotton skeins. padded in the usual manner with washing the anilide or 2,3-hydroxy-naphthoie acid, were thevgeneml degelgped in a diazl? bag; prepared-as follows: X-CONH-arylene-NH:

8. parts of 4- exa drobenzoylamino-l-am-.' ino-na'phthalene were stirred in 30 parts of hy- "fi i g; P g f i if i sggg i and drochloric acid of 30% strength snd'sso parts of 1 g a i g cold water, and the base diaz'otized with '1 parts are f of sodium nitrite dissolved in 30 parts of water.. 135 5 i g p m The diazo solution was filtered and the mineral I s y or a a e acidity neutralized with sodium acetate. ce era, all of which are well known to one skilled lv After the development and the rmsm in the art. The number of arylamines correg and din to the aforementi ed f ul 1 soaping of the skeins, a dull Bordeaux dyeing of spo-n g on orm 5 good fastness to washing andfair fastness to cee-dingly large and it be understood that light was obtained. The dyestufi has the probable the preceding examples glve only a few structure, 7 sentative compounds selected from this group.

' Numerous other arylamines corresponding to this formula may be used with very satisfactory re- CHPCEH, sults. Among these arylamines mention may be made of the following: a N N co-C Arylamines in which the component repre 26 OH -Q sented by X may be- Cyclohexyl Q Q' I o-, m-, or p-methyl-cyclohexyl 0-, m-, or p-phenyl-cyclohexyl I Example 17 o-, m-, or p-phenoxy-cyclohexyl, 27.8 parts of 4-hexahydrobenzoylamino-2,5- divariogs iggi g i fi raldlcals methoxy-aniline were stirred in 30 parts of hyi or 3 drochloric acid of 30% strength and 350 parts at 7 I aor p-decahydronaphthyl, of cold water, and the base diazotized with '7 Am 1; alkox ar or 10x decmdrona parts of sodium nitrite dissolved in 30 parts of il y y 4 water.. When diazotization was complete the or p4, 2, 3, 4 tetrahydmnaphthyl solution was filtered. 15 parts ofpiperidine-al- 1 2 3 4 5 6 hexah drona hth-l pha-carboxylic acid were dissolved in 50 parts py p y of water containing 10 parts oi sodium carbonate Likewise, numerous compounds may be se-' 0 solution. The diazo solution was added to the lected for the component represented by arylene,

piperidine-alpha-carboxylic acid solution, 101- for example,compoundscontaining ortho-,meta

lowed by sufllcient sodium carbonate solution to or para phenylene radicals. These radicals-may render the mass alkaline to brilliant yellow pabe further substituted by alkyl, alkoxyhhalogen, pers. A diazoimino compound of the probable aryl, aryloxy: and/or other non-solubilizing constitution: p groups. Furthermore, this component-may rep- CHPCH CHr-OHr'. J

OH-CONH N=N cm (a) i CHrC ion-oni is thus produced. The product was isolated by resent other arylene nuclei than those ofthe evaporating the solution to dryness under rephenylene series, for instance, any 01' the various duced pressure. It may be purified to remove 'naphthylene radicals, which radicals may also be inorganic salts by extraction with alcohol, filtrasubstituted by one or more of the aforementioned tion, and removal of the alcohol by evaporation groupsQ- to dryness. Coupling oi the aforementioned diazotized A printing paste was Pr par d rding to the arylamines may take place in aqueous solution or following formula: 1 V suspension, in which case the new dyes are obl Parts tained as insoluble pigments. Also, textile fibers I Dlazoimlno c mpound of Formula A 8.6 may be padded with the ice color coupling com Hide 0! -M yflD ponent, in accordance with well knownmethods,

' Turkey red oil then immersed in diazo solutions prepared from Cau c So a 01! of 30% strenath 5.0 the arylamines described herein, in order to pro- Starch tra aca thickener-"n4 duce the new colors on the fibers. These padded Water heated to 160 In. textile fibers mayalso be printed with pastes containing the diazo salts of the herein described 4 100-0 arylamines, resulting in the production of print- Cotton piece goods were printed'irom an ened patterns with the new dye or in t b- The pigment.wa's filtered, washed and dried. It formed a dark blue powder, which dissolved in concentrated sulfuric acid to a bright blue graved copper roll with the above The printed fabric wasthen subjected to the action of saturated steam containing the vaporsot acetic acid, at a temperature'of about 212'1'. Rapid development of the pattern to a bright blue dyeing results, due to the formation onthe fiber or the dyestufi! oi the formula given in Example 6. The

Ject matter of the presentinvention.

- In addition, these arylamines may be diamtized and converted to soluble derivatives which are stable and non-reactive toward the ice color 15 coupling components under alkaline conditions,

but are hydrolyzed to the parent diazo salts upon treatment with acids at ordinary or elevated or temperature, resulting in the production of the 'newcolors in substance according to the printed pattern. An illustration ofth'ismethod of imparting colors to textile fibers is given in Example 17. Other typical amines which may be substituted for piperidine-alpha-carboxylic acid and the probable formulas of the soluble derivatives produced thereby with the diazo salt of the arylamine referred to in Example 17 are:

, Q5 zoylacetanilide, diaceto-acetyl-tolidine, and so forth.

5. Aryl-methyl-pyrazolones, 3-methyl-5-pyrazolone.

6. Dihydroxy-quinolines. I The dyes produced according to the presen invention form an exceedingly desirable addition to the ice colors now in commercial use. The field of ice colors is quite incomplete in the range of bluish-red, Bordeaux, violet and blue shades. Since the herein described colors are particularly eflicaciousin imparting shades falling within this range they will be of great interest to textile manufacturers. The shades are of excellent fastness. and are quite attractive. Valuable pigments are also obtained by coupling in aqueous solution or suspension.

As many apparently widely different embodiments of this invention may be made without desuch as l-phenyl- 0cm on NHCH 00011 cm 6 s \N-N=N .Nrrco-on cm arco e" mooo-cnl CHrCEa OCHa onion NHCH OH son orb-CE (gm-CH r- --N=N NHCO-OH- on, Ethyl.taurlne" f E/ -,Naosoi-cmc a A cm-c CH: H:CH 5 000B oat-om H- 2 I 0H3 OKs-Q "Praline" on on CHr-CH: H E- Nncm CH8 H3. orb-om Methyl glucamine" These diazoimino compounds when made into. printing pastes with the anilide of 2-3-hydroxynaphthoic acid, printed on the fiber and developed by the action of acid and heat, will result carboxylic acids, such asmethyl-anilines, dianisidine, aand z-hydroxy-naphthalene-3 carboxylic acid 2-hydroxy-carbazole-3-carboxylic acid 2-hydroxy-anthracene-3-carboxylic acid alkylaminoand aryIaminO-Z-hydroXy-naphthalene-3-carboxylic' acids 3-hydroxy-diphenylamine-i-carboxylic acid '7-hydroxy-a-naphthocarbazole-fi-carboxylic acid The arylamides may be prepared from aniline, the toluidines, alkoxyland aryloxyanilines, halogenated anilines, halogenated toluidines, halo-v genated alkoxyand aryloxyanilines, trifiuorothol, and so forth.

3. Alphaand beta-naphthol. 4. 'Acyi-acetyl-derivatives of arylamines and arylene-diamines, such as acetoacetanilide, bento be understood that we do not limit ourselves to the specific embodiments thereof except as.

defined in the appended claims.

We claim:

1. A process for making alkali-insoluble azo dyes which comprisescoupling an ice color coupling component with a diazotized aromatic amine having the following general formula:

XCONH-arylene-NH:

in which X represents a hydroaromatic nucleus, and arylene represents an arylene nucleus.

2. The process of claim 1 wherein the component represented by X is a member of the group consisting of all vl-hydroaromatic, alkoxyhydroaromatic, aralkyl-hydroaromatic, aryl-hydroaromatic, and aryloxy-hydrcaromatic radicals, and the component represented by arylene has a member from the group'consisting of hydrcgen alkyl, alkoxyl and halogen.

3. A process for making alkali-insoiuble'azo dyes which comprises coupling. an ice color coupling component with a diazotized aromatic amine having the following general formula:

xCONHarylene-NI-Ia in which X represents ahydroaromatic nucleus of the cyclohexane or decahydronaphthalene serice, and arylene represents an arylene nucleus of the benzene or naphthalene series.

aromatic, aralkyl-hydroaromatic,

4. A process for making alkali-insoluble azo dyes whim comprises coupling an ice color coupling component selected from the group consisting of arylamides o1 2,3-hydroxy-naphthoic acid, 2'hydroxy-carbazo1e-3-carboxylic acid, 2-hydroxy-ant-hracene-3-carboxylic acid, 7-hydroigva-naphthocarbazole 6 carboxylic acid, betanaphthol and acyl-acetyl derivatives of arylamines and arylene-diamines, with a diazotized aromatic amine having the following general i'ormuia:

' X-CONH-arylne-NH:

in which X represents a hydroaromatic nucleus of the cyclohexane or decahydronaphthalene series, and :i ylene represents an arylene nucleus of the benzene or naphthalene series.

5. A process for making alkali-insoluble azo dyes which comprises coupling an arylamide o1 2,3-hydroxy-napnthoio acid with a diazotized aromatic amine having the following general for- X-CONH-arylene-NH:

in which X represents a hydroaromatic nucleus of the cyclohexane series, and arylene represents an arylene nucleus of the benzene series.

6. A process for making an alkali-insoluble azo dye which comprises coupling diazotized N -hexahydrobenzoyl p phenylene-diamine with the heta-napnthalide of 2,3-hydroxy-naphthoic acid. 7 A process for making an alkali-msoluble azo dye which comprises coupling diazotized 4-hexahydrobenzoyl-amino-2,5-dimethoxy-aniline with the ZLIlllidG oi 2,3-hydroxy-naphthoic acid.

8. A process for making an alkali-insoluble azo dye which comprises coupling diazotized 5-hexahydrobenzoyl' amino-2-methyl aniline with diacetoacetyl-o tolidine.

9. Alkali-insoluble azo dyes having the tollowing general formula:

in which X represents a hydroaromatic nucleus, arylene represents an arylene nucleus, and A represents the residue of an ice color coupling component'.

10. The dyes described in claim 9 wherein the component, represented by x is one of a group.

consisting of alkyl-hydroaromatic, alkoxy hydroaryl-hydroaromatic radicals and aryloxy-hydroaromatic. and the component represented by arylene a member from the group consisting or hydrogen, alkyl, alkoxyl, and halogen.

11. Alkali-insoluble azo dyes lowing general formula:

in which X represents a hydroaromatic nucleus of the cyclohexane or decahydronaphthale'ne series, arylene represents an arylene nucleus of the benzene or naphthalene series, and A represents the residue 01 an ice color coupling component.

12. Alkali-insoluble azo dyeshaving the following general formula:

in which X represents a hydroaromatic nucleus oi. the cyclohexane series, arylene represents an arylene nucleus of the benzene series, and A represents the residue of an-arylamide of 2,3-hydroxy-naphthoic 1 n gen,

on care 5 001mm Q r mula: having the Iol- 13. A am dye having tho following formula:

- OHr-OH:

14. Ana-so dye having the following formula:

. 15 v Nnc o- -on cm on cm 15. An azo dye having the following formula:

CHr-OH:

NHOO-O cm om-om 16. Azo dyes having the iollowing general ior-- mula:

in which X represents a hydroaromatlc nucleus, arylene represents an arylene nucleus, and A represents an azo coupling component.

17. Azo dyes having the following general for-- x-corm-si-ylene-N=n-A CHI-OH:

19. A process for making water-insoluble aso dyes which comprises coupling an arylamlde of 7 2,3-hvdroxy-n'aphthoic acid with the diazo comof an aromatic amine having the following gen- I pound of an aromatic amine having the following eral formula:

general formula: CHFCH,

oguk i CHz-CH: on, CH-CONH-GNH: 5

H2O CHCONH NH: CHr-CH: (k

. Alkyl), CHz-CHz OAlkyl 23. A process for making water-insoluble azo 20. An azo dye having the following formula: dyes which comprises coupling an anilide of 2,3-

/CH:CH1\

on, CH'-CONH :V N=N I CHrCH J) 1 Alkvl): 0H IS GONE M71 21. An azo dye having the following formula: hydr'oxy-naphthoic acid with the diazo compound 0mm of an aromatic amine having the following gen- /CH:CH eral formula;

on, CH-CONlI N=,N OAlkyl cat-on, 6

t Alkyl OH H: err-com: NH: -CONH Aryl cHf-c Alkyl 25 22. A process for making water-insoluble azo MILES A. DAHLEN. dyes which comprises coupling an anilide of 2,3- ROBERT E. ETZELMILLER.

hydroxy-naphthoic acid with the diazo compound 

